CN102430315A - Process for recycling 1-fluorotrichloromethane from insulating materials of refrigeration appliances - Google Patents
Process for recycling 1-fluorotrichloromethane from insulating materials of refrigeration appliances Download PDFInfo
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- CN102430315A CN102430315A CN2011103093004A CN201110309300A CN102430315A CN 102430315 A CN102430315 A CN 102430315A CN 2011103093004 A CN2011103093004 A CN 2011103093004A CN 201110309300 A CN201110309300 A CN 201110309300A CN 102430315 A CN102430315 A CN 102430315A
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- fluoro trichloromethane
- precooling
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Abstract
The invention discloses a process for recycling 1-fluorotrichloromethane from insulating materials of refrigeration appliances, comprising the following steps: crushing the insulation materials; reducing the temperature of waste gas, and removing the dust; executing the absorption treatment of the activated-charcoal adsorption bed; executing the electrolytic treatment of low-pressure steam; first-grade condensing; executing the aeration treatment; second-grade condensing; and separating liquid. The invention can realize the high-efficiency recover of the 1-fluorotrichloromethane and can ensure that the waste gas after being processed reaches the discharge standard.
Description
Technical field
The invention belongs to waste electrical equipment recovery technology field, the recovery processing technique of 1-fluoro trichloromethane in particularly a kind of electric refrigerator insulation material.
Background technology
At present, the waste gas that produces in the process of disassembling of waste refrigerating electric appliances contains the plastic foamed panel crushing process of harmful substance freon, particularly insulation material, can discharge a large amount of 1-fluoro trichloromethanes.
The 1-fluoro trichloromethane is claimed refrigerant-11 (R11) again, and molecular formula is CCl
3F, molecular weight 137.5, this is as colourless liquid or gas, and fusing point is-111 ℃, and boiling point is 23.7 ℃, is slightly soluble in water, and chemical stability is good.The 1-fluoro trichloromethane can be used as refrigerant, the foam plastic foaming agent is used, and wherein, the 1-fluoro trichloromethane that discharges in the electric refrigerator insulation material crushing process uses as blowing agent.
The 1-fluoro trichloromethane is a kind of of freon, and atmospheric ozone layer is had lasting destructive power, a CCl
3The chlorine atom that the F molecule discharges can destroy 10
5Individual ozone molecule.Therefore, the tail gas of waste electrical equipment and plastic foam removal process release could discharge after need be removed the 1-fluoro trichloromethane.
Chinese patent CN101745287A discloses a kind of waste gas reclamation treatment system for waste refrigerating electric appliances and method; Said method may further comprise the steps: a, waste gas is fed the adsorbent equipment of being made up of some activated carbon adsorption beds, the Purge gas after the absorption is discharged by outlet; After b, adsorbent bed are saturated, open and be connected the desorption apparatus on the adsorbent equipment, the waste gas of charcoal absorption; Waste gas behind c, the desorption gets into absorption system, carries out the condensation enrichment; D, the remaining waste gas of absorption system get into adsorbent equipment once more and carry out second adsorption, improve the rate of recovery of waste gas.
Plastic foam is pulverized the recovery method that produces waste gas at present, and yield is low, and energy consumption is high, lacks a kind of high efficiente callback processing method of the 1-of combination fluoro trichloromethane physico-chemical property.
Summary of the invention
The technical issues that need to address of the present invention provide the recovery technology that a kind of electric refrigerator insulation material is pulverized 1-fluoro trichloromethane in the waste gas that produces; Its yield is high, low, the effect stability of energy consumption; Can realize the high efficiente callback of 1-fluoro trichloromethane, and make the waste gas after the processing reach discharge standard.
For solving the problems of the technologies described above, the technical scheme that the present invention adopted is:
The recovery technology of 1-fluoro trichloromethane in the electric refrigerator insulation material may further comprise the steps:
A, in closed container, pulverize insulation material and collect insulation material and pulverize the waste gas that contains the 1-fluoro trichloromethane that produces, to above-mentioned waste gas lower the temperature, dust removal process;
B, use some activated carbon adsorption beds parallel with one another in turn successively, the waste gas after cooling, the dust removal process is carried out adsorption treatment, adsorption treatment finishes, and with the toxic emission after purifying, obtains being adsorbed with the activated carbon adsorption bed of 1-fluoro trichloromethane;
Feed low pressure water vapor in c, adsorption treatment finishes in step b the activated carbon adsorption bed and carry out dissection process, obtain containing the moist steam of 1-fluoro trichloromethane, the activated carbon adsorption bed circulation that dissection process finishes is used for the adsorption treatment of step b;
D, moist steam is fed a condensing plant carry out precooling treatment, precooling temperature is 30～45 ℃, and the moist steam after the precooling obtains containing the precooling steam and the precooling liquid that contains the 1-fluoro trichloromethane of 1-fluoro trichloromethane through gas-liquid separation, and it is subsequent use to collect precooling liquid;
E, precooling steam is fed time condensation equipment carry out condensation process, condensation temperature is 0～10 ℃, obtains containing the condensate liquid of 1-fluoro trichloromethane;
F, steps d gained precooling liquid and step e gained condensate liquid are merged, in the airtight vacuum container, carry out separatory and handle the 1-fluoro trichloromethane of the liquid state that obtains.
Improvement of the present invention is: with air heat to 70～90 ℃, feed in the precooling liquid that said steps d obtains, carry out aeration and handle; Obtain containing the hot-air of 1-fluoro trichloromethane; With this hot-air lower the temperature handle after, feed the described activated carbon adsorption bed of step b, carry out adsorption treatment.
Aeration according to the invention is handled the device that adopts and is comprised air heater, Aeration fan, aeration plate.
Among the step a according to the invention, after cooling, the dust removal process, the temperature of waste gas is 25～35 ℃.
Adsorption treatment according to the invention is to make waste gas pass through activated carbon adsorption bed with the flow velocity of 0.1～0.8m/s, is filled with granular activated carbon granule in the activated carbon adsorption bed.
Among the step c according to the invention, the pressure of low pressure water vapor is 0.2～0.4MPa, and temperature is 120～150 ℃.
The device that the separatory processing is adopted among the step f according to the invention is the layering groove; The 1-fluoro trichloromethane that obtains is stored in the storage tank; Said layering groove, storage tank outer wall are provided with vacuum heat-insulating layer, and the vacuum of heat-insulation layer is lower than 100Pa, and the temperature in layering groove and the storage tank is lower than 15 ℃.
Because the technological progress of having adopted technique scheme, the present invention to obtain is:
The present invention is directed to each waste and old refrigeration electric appliances when disassembling, insulation material is pulverized the waste gas of discharging, and reclaims the 1-fluoro trichloromethane (R11 freon) of waste gas the inside, reduces the destruction to atmospheric ozone layer.The design utilizes the active carbon of absorption, analysis feature excellence as adsorbing medium, with the absorption of the 1-fluoro trichloromethane in the tail gas, adsorbs saturated activated carbon fiber and resolves with low pressure water vapor, again the 1-fluoro trichloromethane (R11 freon) of condensing and recycling the inside.Complete unit disposes the activated carbon adsorption bed of a plurality of parallel connections, uses in turn, reaches the effect that runs without interruption.
The moist steam that contains the 1-fluoro trichloromethane that parsing obtains, the mode of employing condensed in two stages can conserve energy.The boiling point of 1-fluoro trichloromethane is 23.7 ℃, when the final temperature of condensation is lower than this boiling temperature, just can obtain liquid 1-fluoro trichloromethane.The moist steam temperature that parsing obtains is higher, if directly adopt the cooling medium of low temperature (being lower than 23.7 ℃) to cool off, condensation effect is not good; Adopt the mode of condensed in two stages, 30～45 ℃ of higher precooling temperatures are adopted in a condensation, make the moisture content in the moist steam carry at first condensation liquefaction of a small amount of 1-fluoro trichloromethane; Obtain precooling liquid; Precooling steam gets into time condensation equipment, carries out 0～10 ℃ of cryogenic condensation, makes the liquefaction of remaining a large amount of 1-fluoro trichloromethane and water condensation; After carrying out the separatory processing again, obtain liquid 1-fluoro trichloromethane.In the precooling liquid that a condensation obtains, feed hot-air and carry out aeration and handle, make 1-fluoro trichloromethane residual in the precooling liquid volatilization of being heated, again the hot-air feeding activated carbon adsorption bed that contains the 1-fluoro trichloromethane that aeration obtains is adsorbed once more.Adopt above-mentioned processing method, can improve condensation effect, realized the high efficiente callback of 1-fluoro trichloromethane, and can energy savings, good feasibility and economy had.
Insulation material pulverized the waste gas obtain is lowered the temperature, dust removal process, help the absorption of 1-fluoro trichloromethane and,, be more conducive to the absorption of 1-fluoro trichloromethane after therefore cooling is handled because of 1-fluoro trichloromethane boiling point is lower to the protection of activated carbon adsorption bed.Dissection process adopts 120～150 ℃ low pressure water vapor, and the pressure of water vapour is 0.2～0.4MPa, and the parsing effect is good, and adsorbent bed is had good protective action.The precooling liquid aeration that the one-level condensation obtains is handled and adopted 70～90 ℃ hot-air, utilizes the heating of hot-air to the 1-fluoro trichloromethane, and the latter is evaporated, and is respond well.After the time condensation, adopt the layering groove to carry out separatory and handle, the 1-fluoro trichloromethane fluid storage that obtains is in storage tank.Layering groove and storage tank all are provided with vacuum heat-insulating layer, help keeping the low temperature environment of container, thereby help keeping the stable in properties of 1-fluoro trichloromethane, improve separating effect, prolong memory time.
Description of drawings
Fig. 1 is a process chart of the present invention.
The specific embodiment
Below in conjunction with specific embodiments the present invention is explained further details:
Embodiment 1
The electric refrigerator insulation material of certain waste electrical equipment treatment plant is handled.Insulation material is ground into particle in closed container, in the crushing process,, collects the waste gas that contains the 1-fluoro trichloromethane, above-mentioned waste gas is handled through being arranged on the outlet of container top.Treatment process may further comprise the steps:
A, to waste gas lower the temperature, dust removal process.Wherein, the temperature of cooling back waste gas is 30 ℃.
B, use three activated carbon adsorption beds parallel with one another in turn, the waste gas after cooling, the dust removal process is carried out adsorption treatment,, after one of them adsorbent bed absorption is saturated, change another adsorbent bed the toxic emission that adsorption treatment finishes.The adsorption treatment method is to make waste gas pass through activated carbon adsorption bed with the flow velocity of 0.5m/s.Wherein, the activated carbon granule that loads in the activated carbon adsorption bed is 50 orders.
C, in step b, adsorbed in the saturated activated carbon adsorption bed and to feed low pressure water vapor and carry out dissection process, obtained containing the moist steam of 1-fluoro trichloromethane, the activated carbon adsorption bed circulation that dissection process finishes is used for the adsorption treatment of step b; Wherein, the temperature of low pressure water vapor is 130 ℃, and pressure is 0.3MPa.
D, moist steam is fed a condensing plant carry out precooling treatment, precooling temperature is 35 ℃, and the moist steam after the precooling obtains containing the precooling steam and the precooling liquid that contains the 1-fluoro trichloromethane of 1-fluoro trichloromethane through gas-liquid separation, reclaims precooling liquid subsequent use.
E, above-mentioned precooling steam is fed time condensation equipment carry out condensation process, condensation temperature is 5 ℃, the condensate liquid that obtains containing the 1-fluoro trichloromethane with purify after tail gas, with the exhaust emissions after purifying;
F, adopt the layering groove that the condensate liquid of the precooling liquid of steps d gained and step e gained is carried out separatory to handle, obtain liquid 1-fluoro trichloromethane and feed in the storage tank.Wherein, layering groove and storage tank all adopt the vacuum heat-preserving mode, and the control temperature inside is lower than 15 ℃, keep airtight in the operating process, prevent the volatilization of 1-fluoro trichloromethane.
The content of 1-fluoro trichloromethane is lower than 100ppm in the waste gas that adsorption treatment finishes, and after recovery finished, the yield that records the 1-fluoro trichloromethane was 98.5%.
Embodiment 2
The difference of present embodiment and embodiment 1 is:
In the steps d, the hot-air that in precooling liquid, feeds 80 ℃ carries out the aeration processing, and residual 1-fluoro trichloromethane is evaporated, and will carry the activated carbon adsorption bed that feeds among the step b after the hot-air cooling of 1-fluoro trichloromethane again and carry out adsorption treatment once more.Wherein, the device of aeration processing employing comprises air heater, Aeration fan, aeration plate.
Among the step f, the condensate liquid that only step e is obtained carries out separatory to be handled, and obtains liquid 1-fluoro trichloromethane and feeds in the storage tank.
The related process parameter of other step is following:
The cooling treatment temperature is 25 ℃ among the step a; The flow velocity of waste gas is 0.1m/s among the step b; The temperature of step c mesolow water vapour is 120 ℃, and pressure is 0.2MPa; The temperature of a condensation is 30 ℃ in the steps d, and the hot air temperature that aeration is handled is 80 ℃; The temperature of time condensation is 0 ℃ among the step e.After recovery finished, the yield that records the 1-fluoro trichloromethane was 99.0%.
Embodiment 3
The difference of present embodiment and embodiment 2 is:
The cooling treatment temperature is 35 ℃ among the step a; The flow velocity of waste gas is 0.8m/s among the step b; The temperature of step c mesolow water vapour is 150 ℃, and pressure is 0.4MPa; The temperature of a condensation is 45 ℃ in the steps d, and the hot air temperature that aeration is handled is 90 ℃; The temperature of time condensation is 10 ℃ among the step e.After recovery finished, the yield that records the 1-fluoro trichloromethane was 99.3%.
Embodiment 4
The difference of present embodiment and embodiment 2 is:
The cooling treatment temperature is 31 ℃ among the step a; The flow velocity of waste gas is 0.6m/s among the step b; The temperature of step c mesolow water vapour is 135 ℃, and pressure is 0.3MPa; The temperature of a condensation is 42 ℃ in the steps d, and the hot air temperature that aeration is handled is 70 ℃; The temperature of time condensation is 4 ℃ among the step e.After recovery finished, the yield that records the 1-fluoro trichloromethane was 99.5%.
In the foregoing description, the number of the activated carbon adsorption bed of step b can also be two or greater than three.
Claims (7)
1. the recovery technology of 1-fluoro trichloromethane in the electric refrigerator insulation material is characterized in that may further comprise the steps:
A, in closed container, pulverize insulation material and collect insulation material and pulverize the waste gas that contains the 1-fluoro trichloromethane that produces, to above-mentioned waste gas lower the temperature, dust removal process;
B, use some activated carbon adsorption beds parallel with one another in turn successively, the waste gas after cooling, the dust removal process is carried out adsorption treatment, adsorption treatment finishes, and with the toxic emission after purifying, obtains being adsorbed with the activated carbon adsorption bed of 1-fluoro trichloromethane;
Feed low pressure water vapor in c, adsorption treatment finishes in step b the activated carbon adsorption bed and carry out dissection process, obtain containing the moist steam of 1-fluoro trichloromethane, the activated carbon adsorption bed circulation that dissection process finishes is used for the adsorption treatment of step b;
D, moist steam is fed a condensing plant carry out precooling treatment, precooling temperature is 30～45 ℃, and the moist steam after the precooling obtains containing the precooling steam and the precooling liquid that contains the 1-fluoro trichloromethane of 1-fluoro trichloromethane through gas-liquid separation, and it is subsequent use to collect precooling liquid;
E, precooling steam is fed time condensation equipment carry out condensation process, condensation temperature is 0～10 ℃, obtains containing the condensate liquid of 1-fluoro trichloromethane;
F, steps d gained precooling liquid and step e gained condensate liquid are merged, in the airtight vacuum container, carry out separatory and handle the 1-fluoro trichloromethane of the liquid state that obtains.
2. the recovery technology of 1-fluoro trichloromethane in the electric refrigerator insulation material according to claim 1; It is characterized in that: with air heat to 70～90 ℃, feed in the precooling liquid that said steps d obtains, carry out aeration and handle; Obtain containing the hot-air of 1-fluoro trichloromethane; With this hot-air lower the temperature handle after, feed the described activated carbon adsorption bed of step b, carry out adsorption treatment.
3. the recovery technology of 1-fluoro trichloromethane in the electric refrigerator insulation material according to claim 2 is characterized in that: said aeration is handled the device that adopts and is comprised air heater, Aeration fan, aeration plate.
4. the recovery technology of 1-fluoro trichloromethane in the electric refrigerator insulation material according to claim 2 is characterized in that: among the said step a, after cooling, the dust removal process, the temperature of waste gas is 25～35 ℃.
5. the recovery technology of 1-fluoro trichloromethane in the electric refrigerator insulation material according to claim 4; It is characterized in that: said adsorption treatment is to make waste gas pass through activated carbon adsorption bed with the flow velocity of 0.1～0.8m/s, is filled with granular activated carbon granule in the activated carbon adsorption bed.
6. the recovery technology of 1-fluoro trichloromethane in the electric refrigerator insulation material according to claim 5 is characterized in that: among the said step c, the pressure of low pressure water vapor is 0.2～0.4MPa, and temperature is 120～150 ℃.
7. according to the recovery technology of 1-fluoro trichloromethane in each described electric refrigerator insulation material of claim 1～6; It is characterized in that: the device that the separatory processing is adopted among the said step f is the layering groove; The 1-fluoro trichloromethane that obtains is stored in the storage tank, and said layering groove, storage tank outer wall are provided with vacuum heat-insulating layer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110309300.4A CN102430315B (en) | 2011-10-13 | 2011-10-13 | Process for recycling 1-fluorotrichloromethane from insulating materials of refrigeration appliances |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110309300.4A CN102430315B (en) | 2011-10-13 | 2011-10-13 | Process for recycling 1-fluorotrichloromethane from insulating materials of refrigeration appliances |
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| CN102430315A true CN102430315A (en) | 2012-05-02 |
| CN102430315B CN102430315B (en) | 2014-07-23 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD204401A1 (en) * | 1981-12-05 | 1983-11-30 | Dessau Magnetbandfab | METHOD FOR THE CONTINUOUS RECOVERY OF VAPORULATED ORGANIC SOLVENTS |
| US5149342A (en) * | 1991-04-17 | 1992-09-22 | Calgon Carbon Corporation | System for recovering solvents and disposing of contaminants released by regeneration of solvent laden air adsorber vessels |
| CN1546204A (en) * | 2003-12-05 | 2004-11-17 | 李光球 | Exhaust gas reclaiming process and apparatus in package printing industry |
| CN101125274A (en) * | 2006-08-17 | 2008-02-20 | 蔡志煌 | Method for recovering organic waste gas |
| CN101439236A (en) * | 2008-12-12 | 2009-05-27 | 江苏迈克化工机械有限公司 | Device for executing recovery processing of organic discharge gas produced in coating procedure |
| CN101745287A (en) * | 2010-01-20 | 2010-06-23 | 广州电器科学研究院 | Waste gas reclamation treatment system for waste refrigerating electric appliances and method |
| CN201871526U (en) * | 2010-10-28 | 2011-06-22 | 仁新设备制造（四川）有限公司 | Recovery device of freon in polyurethane foam of waste refrigerator |
-
2011
- 2011-10-13 CN CN201110309300.4A patent/CN102430315B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD204401A1 (en) * | 1981-12-05 | 1983-11-30 | Dessau Magnetbandfab | METHOD FOR THE CONTINUOUS RECOVERY OF VAPORULATED ORGANIC SOLVENTS |
| US5149342A (en) * | 1991-04-17 | 1992-09-22 | Calgon Carbon Corporation | System for recovering solvents and disposing of contaminants released by regeneration of solvent laden air adsorber vessels |
| CN1546204A (en) * | 2003-12-05 | 2004-11-17 | 李光球 | Exhaust gas reclaiming process and apparatus in package printing industry |
| CN101125274A (en) * | 2006-08-17 | 2008-02-20 | 蔡志煌 | Method for recovering organic waste gas |
| CN101439236A (en) * | 2008-12-12 | 2009-05-27 | 江苏迈克化工机械有限公司 | Device for executing recovery processing of organic discharge gas produced in coating procedure |
| CN101745287A (en) * | 2010-01-20 | 2010-06-23 | 广州电器科学研究院 | Waste gas reclamation treatment system for waste refrigerating electric appliances and method |
| CN201871526U (en) * | 2010-10-28 | 2011-06-22 | 仁新设备制造（四川）有限公司 | Recovery device of freon in polyurethane foam of waste refrigerator |
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| CN102430315B (en) | 2014-07-23 |
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Owner name: SHIJIAZHUANG TENGTAI ENVIRONMENTAL PROTECTION EQUI Free format text: FORMER OWNER: ZHAO SHENG Effective date: 20150109 |
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Effective date of registration: 20150109 Address after: 050000 Hebei city of Shijiazhuang Province Shi Qing Lu No. 199 B 19-2 Patentee after: SHIJIAZHUANG CITY TENGTAI ENVIRONMENTAL PROTECTION EQUIPMENT CO., LTD. Address before: 050000 Hebei city of Shijiazhuang Province Shi Qing Lu No. 199 tengtai environmental protection equipment Co. Patentee before: Zhao Sheng |
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